Free amine-containing polymeric dyes

Abstract

Soluble polymeric colorants composed of free amine groups and chromophoric groups covalently bonded to an organic backbone are disclosed. The number of free amine groups is not less than one-half the number of chromophoric groups. The colorants are characterized by being free of sulfonate, phosphonate and carboxylate groups. The preparation and use of these colorants is also disclosed.

Description

EXAMPLE I

Preparation of poly(vinylamine) backbone

A. Preparation of Vinylacetamide

To 2304 g of acetamide (technical) in a 12 liter reaction flask was added 62.2 ml of 6 M aqueous sulfuric acid followed immediately by 661 g of acetaldehyde (99+%). This mixture was stirred and heated until the internal temperature reached 78.degree. C. (11 minutes) at which point the clear solution spontaneously crystallized, causing a temperature rise to 95.degree. C. The reaction product, ethylidene-bis-acetamide, was not separated. Heating and stirring were continued for another 5 minutes to a temperature of 107.degree. C. and a mixture of 150 g calcium carbonate (precipitated chalk) and 150 g of Celite.RTM. diatomaceous earth powder was added. A first distillate fraction of water and acetamide was removed. The remaining material was transferred to a 22 liter flask and cracked at 35 mm Hg and 185.degree. C. A fraction made up of vinylacetamide and acetamide, was taken overhead and pooled with seven other previously prepared batches. This pooled material was analyzed by NMR and found to contain 5.77 kg of vinylacetamide and 2.45 kg of acetamide.

B. Polymerization of Vinylacetamide

The vinylacetamide-acetamide mixture of Part A was mixed with 4.1 l of isopropanol and chilled overnight. Crystallized acetamide was removed by filtration. The filtrate plus rinses were diluted to a total isopropanol volume of 30.58 l. This solution was placed in a 50 l flask, deoxygenated and heated to 88.degree. C. Then a solution of 233 g of AIBN polymerization catalyst in 830 ml of acetone was added and the mixture was stirred at temperature for about 4 hours to complete polymerization. The resulting thick solution was stripped of solvent to a volume of 15.3 liters and then poured into 95 l of stirred acetone. The polymer formed a precipitate which was recovered by filtration, rinsed with acetone, and dried at 50.degree. C. in a vacuum oven. The final product was 5 kg of poly(vinylacetamide) of a molecular weight of 30,000.

C. Hydrolysis of Poly(vinylacetamide) to Poly(vinylamine hydrochloride)

The poly(vinylacetamide) obtained in Part B (4.97 kg) was dissolved in 5.85 l of water with heating in a 50 l flask. Concentrated hydrochloric acid (5.85 l) was added and the resulting solution was stirred and heated at a gentle reflux (97.degree.-106.degree. C.) for 23 hours. A precipitate formed and was redissolved by addition of 1,170 ml of water. Reflux was continued and over the next 17 hours, 1,000 ml of water was added in several portions to maintain solubility of the polymer. After a total of 40 hours at reflux, the polymer was precipitated by the addition of 5.85 l of concentrated hydrochloric acid. A thick polymeric gum was isolated by decantation and dried under vacuum at 50.degree.-100.degree. C. with occasional pulverization for 56 hours to give 3.1 kg of poly(vinylamine hydrochloride) as a granular solid.

EXAMPLE II

Preparation of poly(N-methylvinylamine)

A. Formation of bis-acetylate

The preparation of poly(N-methylvinylamine) was begun by adding 250 g of N-methylaminoethanol to 691 g (2.20 equivalents) of acetic anhydride at 115.degree.-120.degree. C. The reaction was very exothermic (cooling required) and was complete by the time the addition was concluded. The bis-acetylated product, ##STR49## was isolated by vacuum distillation (bp 95.degree.-98.degree./0.1 mm) as a colorless oil in 93% yield.

B. Pyrolyses of bis-acetylate

The bis-acetylated product of Step A was pyrolyzed by passing 642 g of this material at a rate of 1.17 g/min through a Pyrex.sup.R helices-packed quartz tube (3.5 cm diameter, 40 cm length) maintained at 480.degree.. A 400 ml/min argon stream was employed. The crude pyrolysate was a dark orange oil weighing 629 g. The crude mixture containing the desired N-methylvinylacetamide was distilled (72.degree. C./20 mm) to afford 119 g (30%) of purified N-methylvinylacetamide.

C. Polymerization

Polymerization of 75 g of purified N-methylvinylacetamide was carried out in 150 ml of methanol at 70.degree. C. in the presence of 4 mol % of AIBN. The polymerization was complete within 12 hours and afforded 72 g (96% yield) of poly(N-methylvinylacetamide).

D. Hydrolysis

The polymeric amide of Step C was hydrolysed with 6 N HCl at 125.degree. to yield poly(N-methylvinylamine) as the hydrochloride. This material had a molecular weight of about 20,000 as determined by gel permeation chromatography comparisons to standards. The hydrolysis was monitored by NMR and required roughly 40 hours to go to completion. The product was isolated in essentially quantitative yield by precipitation of the partially evaporated reaction mixture from isopropanol.

EXAMPLES III AND IV

Preparation of high and low molecular weight poly(vinylamine hydrochloride)

The polymerization of vinylacetamide set forth in Step B of Example I was repeated twice on a smaller scale and varying reaction conditions to change the product molecular weight.

In Example III, the relative amount of AIBN polymerization catalyst was reduced by a factor of four, the reaction temperature was lowered to 63.degree. C. and the reaction time was increased to 87 hours. The product was recovered as in Example I, Step B and found to have a molecular weight of 110,000. This material was hydrolyzed to poly(vinylamine) hydrochloride by the method of Example I, Step C.

In Example IV, the relative volume of isopropanol solvent employed was doubled. This reduced the average molecular weight of the poly(vinylacetamide) product to 20,000. The poly(vinylacetamide) was hydrolyzed to poly(vinylamine) in accordance with the process of Example I, Step C.

EXAMPLE V

Preparation of poly(.alpha.-methylvinylamine)

A. Preparation of 2-Amino,2-Cyano-Propane

85.1 g (1 mole) of acetone cyanohydrin is placed in a 2 l pressure vessel and the temperature is raised to 75.degree. C. The pressure is raised to 25 psi with NH.sub.3 gas and is maintained there until the pressure no longer drops (approximately 45 minutes). The crude product is then distilled to afford 46.5 g (0.55 mole, 55%) of product as a colorless oil, bp 58.degree.-60.degree./20 mm.

B. Preparation of 2-Acetamido-2-Cyano-Propane

46.0 g (0.55 mole) of the aminonitrile is added to 67 g (1.20 equiv.) of Ac.sub.2 O with stirring at 80.degree.. After 10 minutes the crude product is vacuum distilled to afford 55.9 g of a yellow solid, bp 115.degree./0.20 mm.

Recrystallization from benzene affords 48.3 g (0.38 mole, 70%) of cream colored needles.

C. Preparation of Isopropenyl Acetamide

Pyrolysis of the acetamido nitrile is carried out by passing 27.6 g (0.22 mmole) through a 4 mm Pyrex.RTM. helix packed quartz column maintained at 600.degree.. The column employed is 3.5 cm in diameter and 40 cm in length. The addition is carried out under a vacuum of 15 mm and the HCN generated is collected in a liquid N.sub.2 trap. The product is 17.5 g of dark yellow solid. Distillation affords 10.4 g (0.10 mole, 48%) of product as a pale yellow crystalline solid, bp 72.degree.-76.degree./0.20 mm.

D. Preparation of Polyisopropenyl Acetamide

5.0 g (43.9 mmole) of 89% pure isopropenyl acetamide is refluxed for 60 hours under Ar in 15 ml of MeOH containing 144 mg of AlBN. The product is isolated by precipitation from acetone to afford 1.39 g (28%) of a white powder. The molecular weight is 2,000.

E. Preparation of Polyisopropenyl Amine

300 mg (3.03 mmole) of the above material is refluxed for 24 hours in 20 ml of 6 N HCl under Ar. The reaction solvent is removed to afford 0.42 g of product. Analysis indicated it to be 73% deacetylated.

EXAMPLE VI

Preparation of Poly(N-butyl vinylamine)

A. Formation of bis-acetate

117 g (1 mole) of N-n-butylaminoethanol is treated with 225 g (2.2 mole) of Ac.sub.2 O at 100.degree. for 4 hours. The bis-acetate is obtained by vacuum distillation in about 82% yield.

B. Pyrolysis of bis-acetate

The bis-acetate product of Step A is pyrolyzed by passing 100.5 g (0.5 mole) of this material at a rate of 1.25 g/min through a Pyrex.RTM. helices-packed quartz tube (3.5 cm.times.40 cm) maintained at 495.degree.. A 400 ml/min Ar stream is employed. The crude pyrolysate is a brownish-orange oil weighing 87.3 g. The crude mixture containing the desired N-n-butylvinylacetamide is distilled (96.degree./20 mm) to afford 30.3 g (43%, 0.22 mole) of product.

C. Polymerization

A sample of 25.0 g (0.18 mole) of purified vinylacetamide from Step B above is polymerized in 60 ml of MeOH at reflux in the presence of 4 mole % AlBN. The polymerization is complete within 18 hours and afforded 23 g (92%) of poly(N-n-butylvinylacetamide). The product is isolated by precipitation from ether and the molecular weight is determined to be about 38,000.

D. Hydrolysis

The polymeric amide of Step C is hydrolyzed with 10 parts by weight of 6 N HCl at 125.degree.. The yield of poly(N-n-butylvinylamine) as the hydrochloride salt is quantitative. The hydrolysis, which is monitored by NMR, requires about 60 hours to reach completion. The product is isolated by precipitation of the partially evaporated reaction mixture from isopropanol.

EXAMPLE VII

Preparation of a Red Colorant

A. Preparation of 1-nitro-2-methylanthraquinone

To a 1 liter flask was added 100 g (0.45 mole) of 2-methylanthraquinone and 500 ml of 96% H.sub.2 SO.sub.4. The mixture was stirred until it was entirely homogeneous and then cooled to 0.degree. C. The addition of 50.5 g (0.50 mole) of KNO.sub.3 was then carried out in ten portions in such a way that the temperature did not rise above 5.degree. C. This required two hours. A yellow product precipitated out after roughly half the KNO.sub.3 had been added.

The yellow slurry was then stirred at 0.degree. C. for 20 hours and poured into 12 l of ice/H.sub.2 O with vigorous stirring. Stirring was stopped, the precipitate was allowed to settle, and the liquid was removed. The precipitate was washed with water until the pH of the wash water was pH 4-5.

An aqueous slurry of the precipitate (2.5 liters in volume) was placed in a 5 liter flask. 100 g of Na.sub.2 SO.sub.3 were added and the mixture was heated and stirred at 95.degree. C. for three hours. The slurry was filtered. The solids were washed with boiling H.sub.2 O and sucked dry. The product was shown to be 1-nitro-2-methylanthraquinone.

B. Preparation of 1-amino-2-methylanthraquinone

The wet filter cake of 1-nitro-2-methylantraquinone (0.45 mole) was placed in a 5 l flask. To the flask was added 420 g (1.75 mole) of Na.sub.2 S.9H.sub.2 O dissolved in 2.5 l of H.sub.2 O and the slurry was heated and then stirred at 95.degree.-99.degree. C. for 2 hours. The reaction mixture was filtered and the orangish-red solid 1-amino-2-methylanthraquinone product was washed with hot H.sub.2 O until the filtrate was clear and dried in vacuo at 70.degree. C.

C. Preparation of 1-amino-2-methyl-4-bromoanthraquinone

Into a 250 ml flask was added 10 g (42.2 mmole) of 1-amino-2-methylanthraquinone of Part B and 150 ml of glacial acetic acid. The mixture was heated to 35.degree. C. and 8.44 g (52.8 mmole) of bromine was added in one portion. After stirring for 20 hours at 35.degree. C., TLC (CHCl.sub.3 on SiO.sub.2) showed 10-20% of residual starting material still remaining.

An additional 1.69 g (0.25 equivalent) of Br.sub.2 was added and the temperature was raised to 50.degree. C. for 4 hours. TLC at this time indicated that the reaction was essentially complete.

The reaction mixture was cooled to room temperature and filtered. The solid product was washed with acetic acid (50 ml) and H.sub.2 O (100 ml).

The wet filter cake was added to 500 ml of hot (80.degree. C.) H.sub.2 O containing 25 g of NaHSO.sub.3 and stirred for 30 minutes at this temperature. The red solid 1-amino-2-methyl-4-bromoanthraquinone was recovered, washed and dried.

D. Preparation of 3'-carbethoxy-2-methyl-4-bromo-1,9-anthrapyridone

With magnetic stirring, two mmoles (630 mg) of the bromoanthraquinone prepared in Part C were treated with 4.02 g (26 mmole) of diethyl malonate and 9 mg of Na.sub.2 CO.sub.3 for two hours at 180.degree.-190.degree. C. Volatiles were removed with an argon stream. After cooling, the product was filtered and the residue was washed with alcohol, hot water, and alcohol again and stirred overnight with 100 ml of toluene. After filtration and drying, the yield was 0.70 g (85%) of solid, 3'-carbethoxy-2-methyl-4-bromo-1,9-anthrapyridone, i.e. ##STR50## This material was not substantially soluble in water. Its solubility was estimated to be less than 50 ppm (basis water).

E. Preparation of a Polymeric Colorant

A 200-ml, one-neck flask was charged with 0.64 g (8 mmol) of the poly(vinylamine hydrochloride) prepared in Example I, 3.4 g (32 mmol) of Na.sub.2 CO.sub.3, and 75 ml of H.sub.2 O. The mixture was stirred until a homogeneous solution (pH 10.7) was obtained and 25 ml of pyridine was added. Then, 1.64 g (4 mmol) of 3'-carbethoxy-2-methyl-4-bromoanthrapyridone, prepared in Step D, was added along with 143 mg (1 mmol) of red Cu.sub.2 O and the mixture was lowered into a bath pre-heated to 120.degree. C. and stirred vigorously at reflux for 30 minutes.

The reaction mixture was filtered, while still boiling hot, through a sintered blass filter and the small amount of residue was washed with 100 ml of H.sub.2 O-pyridine (3:1). A clear solution (200 ml, pH 10.8) of the following red polymeric dye in 3:1 water-pyridine was obtained. ##STR51##

The solution was divided into two equal portions with one portion being purified as is described in Step G below, and the other half being purified as is described in Step H.

F. Purification Of Nonsolubilized Colorant By Dialysis

One-half (100 ml) of the solution obtained in Step E was placed in a regenerated cellulose dialysis bag (average pore radius 24 A, estimated molecular weight cutoff 2.times.10.sup.4) and dialyzed against 4 liters of 25% aqueous pyridine for 72 hours. Following this, dialysis was carried out against 25% aqueous pyridine that was 0.5% by weight NaCl until the polymer completely precipitated (.about.10 days). Dialysis was then carried out against dilute saline solution (72 hours) and finally against pure H.sub.2 O (24 hours). After centrifugation (8000 rpm for one hour) and drying, there was obtained 700 mg of polymeric dye as a fine red powder. This polymeric dye was soluble in water at pHs of from about 2.0 to about 4.0, but otherwise was not substantially water-soluble. n and m were calculated as being equal, i.e., n=m based on feed ratios. By elemental analysis, m was seen to equal 0.95 n.

G. Purification Of Nonsolubilized Colorant By Ultrafiltration

100 ml of the solution obtained in Step F was ultrafiltered with an Amicon Model 202 stirred cell (Amicon Corp., Lexington, Mass.) employing a 62 mm diameter PM 10 membrane (molecular weight cutoff 1.times.10.sup.4). The device was operated at 40 psi Ar pressure. Ultrafiltration was carried out with 2.9 liters (29 diavolumes) of 15% aqueous pyridine made up to 0.02 N in NaOH (pH 12). After ultrafiltration the solution was precipitated onto 50 g of Celite.RTM. which was in 1 liter of rapidly stirred isopropyl alcohol containing 5 ml of acetic acid. The Celite was filtered, washed with isopropyl alcohol (2.times.200 ml) and dried.

The dye was extracted from the Celite by a two-fold treatment (stirred 30 minutes) with 200 ml of H.sub.2 O containing approximately 10 ml of 12 N HCl (pH 2.0). Filtration of the Celite followed by partial evaporation of the solution (pH maintained at 2-3 by the addition of HCl as necessary) and lyophilization provided 540 mg of polymeric dye.

EXAMPLE VIII

Preparation of a red colorant

A. Coupling Of Chromophores

To a solution of 1.87 g (20 mmol-1 equivalent) of the poly(N-methylvinylamine hydrochloride) prepared in Example II, in aqueous ethylene glycol (2:1 glycol/water) containing 4 equivalents of Na.sub.2 CO.sub.3, was added 1/2 an equivalent of the 3'-carbethoxy-2-methyl-4-bromo-1,9-anthrapyridone prepared in Step D of Example VII and 0.2 g of red Cu.sub.2 O. The reaction was completed in 1.5-2 hrs at 110.degree. C. The catalyst and other solid contaminants were removed by filtration to yield a solution of the coupled colorant ##STR52##

B. Workup

The dye was purified in a manner identical to that of Example VII, Part H. The yield of red polymeric product was 3.67 g. Elemental analysis showed m=0.43 and n=0.57.

EXAMPLE IX

A. Preparation of 3'-acetyl-2-methyl-4-bromo-1,9-anthrapyridone

A 100 ml flask was charged with 3.6 g (10 mmole) of the 1-amino-2-methyl-4-bromoanthraquinone of Part C of Example VII, 10 ml (10.2 g, 78.5 mmole) of ethyl acetoacetate and 0.033 g (0.31 mmole) of sodium carbonate. The mixture was heated under a slow argon flow in a 180.degree.-190.degree. C. oil bath with stirring. Lower boiling materials (H.sub.2 O, EtOH, etc.) were distilled off as they were produced. After heating for 1.5 hours, a thin layer chromatogram (silica gel, ethyl acetate) indicated the reaction was complete. The reaction mixture was cooled and filtered. The residue was washed with ethanol, hot water, and ethanol; then the residue was stirred with boiling toluene for 5 minutes and filtered. This process was repeated four times and the final residue was dried in a 44.degree. C. vacuum oven overnight to yield 3.32 g (87% yield) of 3'-acetyl-2-methyl-4-bromo-1,9-anthrapyridone, i.e., ##STR53##

B. Coupling Of Dye Chromophore To A Polymer

A 250-ml, one-neck flask was charged with 0.64 g (8 mmol) of the poly(vinylamine hydrochloride) of Example III, 3.4 g (32 mmol) of Na.sub.2 CO.sub.3, and 75 ml of H.sub.2 O. The mixture was stirred until a homogeneous solution (pH 10.7) was obtained. The solution was then treated with 25 ml of pyridine, 1.53 g (4 mmol) of 3'-acetyl-2-methyl-4-bromoanthrapyridone prepared in Step A of this Example, 143 mg (1 mmol) of red Cu.sub.2 O and lowered into a bath preheated to 120.degree. C.

After refluxing 30 minutes, the reaction mixture was filtered while still boiling hot and the trace of residue washed with 100 ml of 25% aqueous pyridine. This afforded a bright red solution of polymeric dye of the formula ##STR54##

C. Purification

The 200 ml of polymeric dye solution (pH 11.5) were purified by ultrafiltering (9.0 liters of pH 12 15% aqueous pyridine), precipitating onto Celite, washing, and re-extracting into pH 2 H.sub.2 O as described in Example VII, Step G. After lyophilization, there was obtained 480 mg of product. Elemental analysis showed m=0.33 and n=0.67.

EXAMPLE X

A. Preparation of N-Acetyl-1-Methylamino-4-Bromoanthraquinone

A 250 ml flask equipped with a mechanical stirrer was charged with 30 g (95 mmole) of 1-methylamino-4-bromoanthraquinone (purchased from Sandoz), 19.5 g (191 mmole) of acetic anhydride, and 0.23 g of 96% H.sub.2 SO.sub.4. The sludgelike mixture was heated and stirred at 110.degree. for 30 minutes. The reaction mixture was cooled to 0.degree. and 50 ml of H.sub.2 O was added. After stirring 1/2 hour, 55 ml of 30% NaOH was added and the entire mixture was then transferred to a pressure reactor for the following reaction. A TLC (EtOAc) showed only a single product in the reaction.

B. Preparation of 1'-Methyl-4-Bromoanthrapyridone

The acetyl anthraquinone from Part A was placed in a pressure vessel and heated and stirred at 120.degree. for 2 hours. The reaction mixture was cooled, filtered, and washed with H.sub.2 O. After oven drying, the brown solid was dissolved in 200 g of 96% H.sub.2 SO.sub.4 and reprecipitated by the addition of 40 ml of H.sub.2 O. The solid was filtered and washed with 25 g of 78% H.sub.2 SO.sub.4. The filter cake was then stirred with 800 ml of H.sub.2 O, filtered, washed, and dried in vacuo. The solid then obtained was twice recrystallized from trichloroethane to afford 8.5 g of pure anthrapyridone.

C. Polymer Attachment Step

A 250 ml round bottomed flask was charged with 480 mg (6.0 mmole) of poly(vinylamine) of Example I, 2.54 g (24.0 mmole) of Na.sub.2 CO.sub.3, and 36 ml of H.sub.2 O. The mixture was stirred until solution was complete and 72 ml of ethylene glycol was added. Then, 510 mg (1.50 mmole, 0.25 equivalents) of 1'-methyl-4-bromoanthrapyridone was added along with 50 mg of Cu.sub.2 O. The reaction mixture was then placed in a pre-heated oil bath, refluxed for ten minutes, and rapidly filtered. The red polymeric dye obtained in the filtrate is of the following composition. ##STR55##

D. Workup

Purification was carried out by bag dialysis as described in Example VII, Step G. The yield of product was 0.57 g. Elemental analysis showed m=0.23 and n=0.77.

EXAMPLE XI

Preparation of a blue polymeric dye

A. Coupling Of Dye To Polymer

A 250-ml, 3-neck flask, equipped with overhead stirrer, reflux condenser, Ar bubbler, and thermometer, was charged with 1.19 g (15 mmol) of poly(Vinylamine hydrochloride) prepared in Example I and 50 ml of H.sub.2 O. The mixture was stirred until homogeneous and then treated with 0.60 g (15 mmol) of NaOH and 1.6 g (15 mmol) of Na.sub.2 CO.sub.3. The mixture was stirred under Ar until homogeneous (pH 12.6) and then treated with 0.476 g (1.5 mmol) of 1-methylamino-4-bromoanthraquinone, ##STR56## prepared according to C. V. Wilson, Org. Syn., 29, 68 (1949), and 10 mg of Cu.sub.2 Cl.sub.2 as a slurry in 30 ml of pyridine. The reaction mixture was thoroughly deoxygenated with Ar and immersed in a preheated oil bath and refluxed under Ar.

The following treatments were made to the refluxing reaction mixture at the total elapsed times (based on attainment of reflux) indicated:

(a) 60 min, 1.50 mmol bromoanthraquinone, 20 ml pyridine;

(b) 120 min., 1.50 mmol bromoanthraquinone, 5 mg Cu.sub.2 Cl.sub.2, 10 ml pyridine;

(c) 180 min., 1.50 mmol bromoanthraquinone, 10 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH;

(d) 240 min., 1.50 mmol bromoanthraquinone, 5 mg Cu.sub.2 Cl.sub.2, 15 ml pyrydine;

(e) 300 min., 0.75 ml (3 mmol) of 12 N NaOH.

A total of 7.5 mmol of anthraquinone was added and the total volume of the reaction mixture was 135 ml (pyridine: H.sub.2 O/85:50). After 360 minutes, TLC (CHCl.sub.3 on SiO.sub.2) showed that no starting material remained. The polymeric blue colorant was filtered while still boiling not through a sintered glass filter and purified as described in Step B.

B. Purification

Without allowing the solution to cool, the dye was precipitated as rapidly as possible into one liter of rapidly stirred ice-cold acetone containing 20 g of Celite. After stirring ten minutes, the dyed Celite was filtered and washed with acetone (4.times.300 ml). The filtrates contained monomeric species and inorganic salts.

The blue polymeric dye was extracted from the Celite by eight consecutive treatments with one liter of dilute aqueous HCl (pH 2.5). After concentration (HCl added as needed to maintain the pH at 3.0), the solution was freeze-dried to provide 2.06 g of cationic polymeric blue dye. Elemental analysis of the material showed that m=0.48 and n=0.52 such that the product was ##STR57##

EXAMPLE XII

Preparation of a purple polymeric colorant

A. Preparation of Chromophore

Benzanthrone, ##STR58## was vacuum sublimed. A 12.1 g portion (52.7 mmoles) was placed in a flask and dissolved in 50 ml of acetic acid with warming. 9.3 g of neat bromine was added along with 65 ml of additional acetic acid and 30 ml of nitrobenzene. The mixture was stirred and gradually heated--finally being maintained at 90.degree. C. for 12 hours. The reaction mixture had become homogeneously yellow. The mixture was cooled and poured into a liter of water and 500 ml of dichloromethane to yield two phases. The color went to the organic phase which was isolated, dried with Na.sub.2 SO.sub.4, filtered and evaporated to yield a solid chromophore which upon analysis was found to be: ##STR59##

B. Coupling

358 mg (3.81 mmole, 1 equivalent) of the poly(N-methylvinylamine hydrochloride) of Example II and 10 ml of water and 25 ml of ethylene glycol are placed in a 100 ml flask. 1.62 g (15.2 mmole) of sodium carbonate, 0.5 g (0.42 equivalents) of the chromophore of Part A, and 50 mg of a cupric acetate catalyst are added and the mixture is heated to 110.degree. C. and there maintained for 2-3 hours. Solids are removed by filtration to yield a clear ethylene glycol/water solution of the purple colorant ##STR60##

C. Workup

The product is isolated by precipitation onto Celite and extraction into dilute acid as described in Example XI, Step B. The yield of purple polymer is 0.45 g after lyophilization.

EXAMPLE XIII

Preparation of a polymeric orange colorant

A. Preparation of Chromophore

Using the general method disclosed in Patki et al., Indian Journal of Technology, Vol. 12 (1974) p 540-545, 31.6 g (100 mmole) of the anthraquinone product of Example VII, Step C, is suspended in 100 ml of water. Sodium hydroxide (15 g in 60 ml of water) is added with stirring followed by 70 g (1.2 mole) of acetone. The mixture is refluxed for 20 hours. A TLC test indicates that the anthraquinone and acetone have reacted to completion. The mixture is cooled, neutralized with hydrochloric acid, and filtered to recover the yellow precipitate of 2,4-dimethyl-6-bromopyridinanthrone ##STR61## which is washed with water and dried.

B. Coupling

A 100 flask is charged with 0.64 g (8 mmole) of the poly (vinylamine hydrochloride) of Example III, 3.4 g (32 mmole) of Na.sub.2 CO.sub.3, 32 ml of water, and 65 ml of ethylene glycol. Then 1.02 g (3.0 mmole) of the product of Step A, along with a catalyst consisting of 0.25 g of finely powdered cuprous oxide is added and the mixture is stirred at 100.degree.-110.degree. C. for 30 minutes. The reaction mixture is filtered to remove solids and yield an orange glycol/water solution of the polymeric colorant: ##STR62##

C. Workup

The product was purified by bag dialysis vs. aqueous pyridine as described in Example VII, Step G. The yield of polymer as a yellow powder, after filtration and drying, was 0.85 g.

EXAMPLE XIV

A. Chromophore preparation

1-amino-4-bromoanthraquinone, acetoacetic acid ethyl ester and alkane sulfonic acid catalyst are reacted in accordance with the teachings of Example 1 of U.S. Pat. No. 2,759,940 issued Aug. 21, 1956 to Bucheler et al., (which patent is herein expressly incorporated by reference) to yield the yellow chromophore ##STR63##

B. Coupling of Chromophores to Backbone

0.37 g (4 mmole) of the poly(isopropenylamine) hydrochloride prepared in Example V is dissolved in 48 ml of 2:1 ethylene glycol/water along with 1.70 g of Na.sub.2 CO.sub.3. Then, 0.79 g (2 mmole) of the chromophore of Step A is added along with 0.3 g of cupric acetate monohydrate catalyst. The mixture is heated at 100.degree. C. for 40 minutes.

The reaction mixture is filtered to remove solid residues and yield a solution of the yellow polymeric colorant ##STR64##

C. Workup

The product was precipitated by addition to one liter of rapidly stirred acetone containing 20 g of Celite. Thorough extraction of the celite with dilute HCl (pH 3.0), followed by evaporation and freeze-drying, afforded 0.75 g of polymeric yellow colorant.

EXAMPLE XV

A. Preparation of Chromophore

4.4 g (10 mmole) of D&C Orange #4, ##STR65## is reacted overnight at room temperature with an excess of acetic anhydride in pyridine to acetylate the naphthyl hydroxyl group. The acetylated product is recovered, and added to a solution of one equivalent thionyl chloride in 100 ml of benzene containing a catalytic amount of DMF. After stirring for 2 hours at room temperature, the bright orange chlorosulfonyl derivative, ##STR66## is recovered.

B. Coupling of Chromophore to Backbone

7.0 g of the poly(vinylamine hydrochloride) prepared in Example IV is added to a 2000 ml flask, 700 ml of water and 350 ml of tetrahydrofuran are added and the pH is raised from 2.5 to 9.5 by addition of 2.5 N NaOH.

Next 13.7 g (0.4 equivalents, based on total amine polymer) of the chromophore of Part A is slowly added at room temperature while maintaining the pH at 9.0-9.5 by NaOH addition. Additional THF and NaOH are added and the pH is maintained at 9.5-10.5. A final stirring is carried out at pH 12.5-13.0 to complete hydrolysis of the acetyl group. The product is not isolated, but is used immediately for Step C.

C. Workup

All THF was removed by evaporation at reduced pressure to provide a pH 13.0 solution of the following anionic dye. ##STR67##

Ultrafiltration of this solution was then carried out with 15% aqueous pyridine made up to 0.02 N in NaOH (pH 12.0). Roughly 10 diavolumes were required to remove the monomeric impurities. The solution was then precipitated onto 200 g of Celite which was in 10 liters of rapidly stirred acetone containing 100 ml of acetic acid. The Celite was filtered, washed with acetone (4.times.1 liter), and dried.

The dye was extracted from the Celite by five one-hour treatments with 2 liters of dilute HCl (pH 2.0). Evaporation of the solution (pH maintained at 2-3 by the addition of HCl as necessary) and lyophilization provided 15.5 g of brilliant orange polymeric dye. ##STR68##

EXAMPLE XVI

A. Preparation of Chromophore

1. 3'-Carbethoxy-3-Bromo-4-p-Toluidinoanthrapyridone

31.4 g (77.1 mmoles) of 1-amino-2-bromo-4-p-toluidinoanthraquinone (Benzenoid Organics Inc.), 250 ml of diethylmalonate, and 0.63 g of sodium acetate were heated at 180.degree.-185.degree. under an argon stream for 105 minutes. During this period the reaction mixture turned from deep blue to purplish red. The reaction mixture was cooled to 45.degree. and the excess diethylmalonate was removed in vacuo (0.25 mm). The product was dried at 80.degree./0.1 mm for 18 hours and had the following structure: ##STR69##

2. Potassium 3'-Carbethoxy-4-p-Toluidinoanthrapyridone-2-Sulfonate

The crude product from the above reaction (38.8 g, 77.1 mmoles) was refluxed with 40.0 g of K.sub.2 SO.sub.3 in H.sub.2 O/.phi.OH (3:7). The course of the reaction was followed by TLC (5% MeOH/CHCl.sub.3 elution on silica gel). After 48 hours, the reaction was judged complete. The phenol was removed with steam, at which point the product precipitated. The royal purple product was filtered and dried in vacuo to afford 39.7 g of monomeric dye of the following structure: ##STR70##

3. 3'-Carbethoxy-4-p-Toluidinoanthrapyridone-2-sulfonyl Chloride

3.90 g (7.2 mmole) of the above anthrapyridone sulfonate, 83.5 g (0.71 mole) of thionyl chloride, and 25 drops of DMF were stirred at room temperature for 7 days in 100 ml of 1,1,2,2-tetrachloroethane. The excess reagent and solvent were removed by vacuum distillation and the purple residue was dissolved in methylene chloride and filtered to remove KCl. Removal of the solvent and drying in vacuo afforded a quantitative yield (3.76 g) of sulfonyl chloride. ##STR71##

B. Chromophore Attachment (Schotten-Bauman Reaction)

318 mg (4.0 mmoles) of poly(vinylamine) hydrochloride (prepared in Example I) was dissolved in 15 ml of H.sub.2 O and the pH was raised to 10.0 by the addition of 10% NaOH solution.

To the solution was added 349 mg (0.66 mmole) of the anthrapyridone sulfonyl chloride of Part A and 5 ml of ethylene glycol. These additions were repeated twice more over a period of 7.5 hours as the pH was maintained at 9.5-10.5 by the addition of NaOH, as necessary.

C. Workup

The product of this reaction is isolated as follows. ##STR72##

The alkaline aqueous glycol mixture was diluted to a volume of 100 ml with 15% aqueous pyridine made up to 0.02 N with NaOH (pH 12.0) and ultrafiltered with an Amicon Model 202 stirred cell utilizing a PM 10 membrane (molecular weight cutoff 1.times.10.sup.4). After the ultrafiltration had been carried to 10 diavolumes (1.0 liter) with this pyridine solution, the deep purple mixture was precipitated into one liter of rapidly stirred isopropyl alcohol containing 50 g of Celite and 5 ml of acetic acid.

The dye was extracted from the Celite by two 30 minute treatments with 250 ml of H.sub.2 O made to pH 2.0 with HCl. This afforded, after lyophilization, 514 mg of royal purple polymer shown by elemental analysis to have m=0.46 and n=0.54.

EXAMPLE XVII

A. Preparation of Chromophore

1. 3'-Carbethoxy-2-methyl-4-anilinoanthrapyridone

4.12 g (10 mmole) of 3'-carbethoxy-2-methyl-4-bromoanthrapyridone (purchased from Sandoz Colors and Chemicals) was stirred under an inert atmosphere with 25 ml of aniline in a bath maintained at 145.degree.-150.degree.. After 2.5 hrs, TLC (EtOAc on silica gel) indicated the complete disappearance of starting material with the formation of a sole product. Removal of the excess aniline by vacuum distillation followed by drying in vacuo (100.degree./0.1 mm) afforded a quantitative yield of product (4.24 g).

2. Chlorosulfonation

4.00 g (9.43 mmole) of 3'-carbethoxy-2-methyl-4-anilinoanthrapyridone was dispersed in 25 ml of CHCl.sub.3 and the mixture was cooled to 0.degree.. To the mixture was added dropwise over a period of 1 hr 5 equivalents (4.10 g) of chlorosulfonic acid. After stirring at 0.degree. for an additional 1 hr, the reaction mixture was filtered and the product was washed well with CHCl.sub.3 (0.degree.) and then dried in vacuo to afford 4.66 g (8.91 mmoles) of sulfonyl chloride as a violet-red crystalline solid. Elemental analysis confirms the following structure: ##STR73##

B. Coupling

523 mg (1.0 mmole) of the above sulfonyl chloride was treated with 3.0 mmoles (238.5 mmoles) of poly(vinylamine) in 40 ml of THF-H.sub.2 O (1:3) at room temperature and pH 10.5-11.0. This afforded a red polymeric dye with poor water solubility of the following structure: ##STR74##

C. Workup

The THF was removed from the bright red dye solution by rotary evaporation and the mixture was then diluted to a volume of 100 ml with 15% aqueous pyridine made up to 0.02 N with NaOH. The mixture was ultrafiltered to a total of 15 diavolumes (1.5 liters) of this pyridine solution and then precipitated onto 65 g of Celite in 1.5 liters of rapidly stirred isopropyl alcohol containing 25 ml of acetic acid.

Extraction of the dye from the Celite was carried out by two 30 minute treatments with 500 ml of H.sub.2 O made to pH 3.0 with HCl. This afforded, after evaporation and freeze-drying, 643 mg of bright red polymeric dye shown by elemental analysis to have m=0.30 and n=0.70.

EXAMPLES XVIII AND XIX

The preparation of Example VIII is repeated twice varying the backbone employed. In Example XIX, 1.1 equivalent of poly(N-butylvinylamine), as prepared in Example VI, is employed as backbone. In Example XX, poly(.alpha.-methylvinylamine), as prepared in Example X, is employed as backbone.

EXAMPLE XX

A. Preparation of 3'-carboethoxy-2'-methyl-2-methyl-4-bromo-1,9-anthrapyridine

Following the teachings of Bucheler and Peter in U.S. Pat. No. 2,759,940 (cited previously in Example XIV, Step A), 15.8 g (50 mmol) of 1-amino-2-methyl-4-bromoanthraquinone (Example 7, Step C) were heated for three hours at 135.degree.-140.degree. C. with 178.5 g (1.37 mol) of acetoacetic ester and 1.0 ml of methane sulfonic acid. During the course of the reaction, volatiles were removed with a slow stream of Ar. After cooling, the reaction mixture was diluted with ethanol (100 ml), filtered, and the residue washed with ethanol to provide 17.9 g of the following bromoanthrapyridine as a dark brown powder. ##STR75##

B. Preparation of an Orange Dye

A 250-ml, three-neck flask, equipped with overhead stirrer, reflux condenser, Ar bubbler, and thermometer, was charged with 1.19 g (15.0 mmol) of poly(vinylamine hydrochloride) prepared in Example I, 0.60 g (15 mmol) of NaOH, 1.60 g (15 mmol) of Na.sub.2 CO.sub.3, and 50 ml of H.sub.2 O. The mixture was stirred until a homogeneous solution was obtained (pH 12.6), at which point the solution was treated with 615 mg (1.50 mmol) of the anthrapyridine prepared in Part A, 10 mg of Cu.sub.2 Cl.sub.2, and 30 ml of pyridine. The reaction mixture was lowered into a pre-heated bath and stirred at reflux under Ar.

The following treatments were made to the reaction at the times indicated:

(a) 60 minutes, 1.5 mmol bromoanthrapyridine, 20 ml pyridine;

(b) 120 minutes, 1.5 mmol bromoanthrapyridine, 5 mg Cu.sub.2 Cl.sub.2, 10 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH;

(c) 210 minutes, 1.5 mmol bromoanthrapyridine, 10 ml pyridine;

(d) 300 minutes, 1.5 mmol bromoanthrapyridine, 5 mg Cu.sub.2 Cl.sub.2, 20 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH.

After 390 minutes, the reaction mixture was filtered through a sintered funnel while still hot and immediately diluted with 160 ml of boiling pyridine.

C. Workup

The 300 ml of deep orange solution (pyridine: H.sub.2 O, 5:1, pH 12.9) was added as rapidly as possible (no cooling) to 2.5 liters of rapidly stirred ice-cold acetone containing 50 g of Celite. After stirring 15 minutes, the celite was filtered and washed with acetone (4.times.500 ml). The filtrate was examined by TLC and was shown to contain principally monomeric species.

The orange polymeric dye was extracted from the Celite by eight consecutive treatments with one liter of dilute aqueous HCl (pH 3.4). This afforded, after lyophilization, 2.34 g of cationic orange dye. Elemental analysis showed that m=0.42 and n=0.58. ##STR76##

EXAMPLE XXI

A. Preparation of a Blue Dye

A 250-ml, 3-neck flask, equipped with overhead stirrer, reflux condenser, Ar bubbler, and thermometer, was charged with 1.19 g (15 mmol) of poly(vinylamine hydrochloride) prepared in Example I, 0.6 g (15 mmol) of NaOH, 1.6 g (15 mmol) of Na.sub.2 CO.sub.3, and 50 ml of H.sub.2 O. The solution was stirred until homogeneous (pH 12.5) and then treated with 476 mg (1.5 mmol) of 1-amino-2-methyl-4-bromoanthraquinone (Example VII, Step C), 10 mg of Cu.sub.2 Cl.sub.2, and 30 ml of pyridine. The mixture was lowered into a preheated bath (125.degree. C.) and stirred at reflux under Ar.

The following treatments were made to the reaction mixture at the times indicated:

(a) 60 minutes, 1.5 mmol bromoanthraquinone, 20 ml pyridine;

(b) 120 minutes, 1.5 mmol bromoanthraquinone, 5 mg Cu.sub.2 Cl.sub.2, 10 ml pyridine;

(c) 210 minutes, 1.5 mmol bromoanthraquinone, 10 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH;

(d) 300 minutes, 1.5 mmol bromoanthraquinone, 5 mg Cu.sub.2 Cl.sub.2, 20 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH.

A TLC (CHCl.sub.3 on SiO.sub.2) after 390 minutes showed that almost no 4-bromoanthraquinone remained. The mixture was filtered while still boiling hot through a fritted filter and diluted with 160 ml of boiling pyridine.

B. Purification

Without allowing the dye solution to cool, the deep blue solution was precipitated into 2.5 liters of rapidly stirred ice-cold acetone containing 50 g of celite. After stirring for 15 minutes, the celite was filtered and washed thoroughly with acetone (4.times.500 ml). The purplish filtrate contained (TLC analysis) primarily 1-amino-2-methyl-4-hydroxyanthraquinone and a trace of 1-amino-2-methyl-4-bromoanthraquinone which remained unreacted.

The blue polymeric dye was extracted from the celite by ten consecutive 30 minute treatments with one liter of dilute aqueous HCl (pH 2.5). Lyophilization provided 1.98 g of cationic blue polymeric dye. Elemental analysis showed that m=0.44 and n=0.56. ##STR77##

EXAMPLE XXII

A. Preparation of 3'-phenyl-2-methyl-4-bromo-1,9-anthrapyridone

A 250-ml flask, equipped with overhead stirrer, condenser, and Ar inlet was charged with 15.8 g (50 mmol) of 1-amino-2-methyl-4-bromoanthraquinone (Example VII, Step C) and 120 ml of toluene. The mixture was treated with phenylacetyl chloride (8.5 g, 55 mmol) and heated to reflux. After 3.5 hours, the mixture was cooled to 80.degree. and filtered. The filtrate was evaporated to 30 ml and cooled. The deposited dark yellow crystals were filtered, washed with diethylether, and dried to afford 12.5 g of N-phenylacetyl anthraquinone.

This material (4.56 g, 10.5 mmol) was placed in a 100-ml, 3-neck flask equipped with condenser, overhead stirrer, thermowell, and Ar inlet. After 30 ml of 2-methoxyethanol were added, the contents were heated to 122.degree. C. and 0.45 g (8 mmol) of KOH in 0.6 ml of H.sub.2 O was added dropwise over 60 seconds. After stirring for one hour at 120.degree. C., the mixture was cooled to 5.degree. C. and the solid obtained (1.71 g) was filtered. Concentration of the mother liquor and recrystallization of the residue from acetic acid (170 ml) afforded an additional 2.30 g of product. The total yield of anthrapyridone was 4.01 g. ##STR78##

B. Preparation of a Red Polymeric Dye

A 200-ml, one-neck flask was charged with 0.64 g (8 mmol) of poly(vinylamine hydrochloride) prepared in Example I, 3.4 g (32 mmol) of Na.sub.2 CO.sub.3, and 75 ml of H.sub.2 O. The mixture was stirred until a homogeneous solution (pH 10.7) was obtained. 25 ml of pyridine and 1.67 g (4 mmol) of 3'-phenyl-2-methyl-4-bromoanthrapyridone prepared in Step A were added along with 143 mg (1 mmol) of red Cu.sub.2 O and the mixture was lowered into a bath preheated to 120.degree. C. and stirred vigorously at reflux for 180 minutes. The reaction mixture was filtered while still boiling hot and diluted with 100 ml of 15% aqueous pyridine made up to 0.02 N in NaOH.

C. Purification

The red polymeric dye solution (200 ml, pH 12.0) obtained in Step B ##STR79## was ultrafiltered with an Amicon Model 202 stirred cell in conjunction with a PM 10 membrane (molecular weight cutoff 1.times.10.sup.4). Ultrafiltration was carried out with 4.0 liters (20 diavolumes) of 15% aqueous pyridine made up to 0.02 N with NaOH. The red dye solution was then precipitated onto 100 g of celite which was in 2 liters of rapidly stirred isopropyl alcohol containing 10 ml of acetic acid. The celite was filtered, washed with isopropyl alcohol (2.times.400 ml), and dried.

The dye was extracted from the celite by two treatments with 500 ml of dilute aqueous HCl (pH 2.0). This afforded, after freeze-drying, 1.23 g of red polymeric dye. Elemental analysis showed m=0.48 and n=0.52.

EXAMPLE XXIII

A. Preparation of 3'-carbethoxy-2'-methoxy-2-methyl-4-bromo-1,9-anthrapyridine

A 500-ml, 3-neck flask, equipped with overhead stirrer, thermometer, and Ar bubbler, was charged with 4.12 g (10 mmol) of 3'-carbethoxy-2-methyl-4-bromoanthrapyridone prepared in Example VII, Step D, and 200 ml of dry N,N-dimethylformamide. Stirring was begun and the mixture was heated to 40.degree. and thoroughly deaerated with Ar. The mixture was then treated with 1.38 g (10 mmol) of anhydrous K.sub.2 CO.sub.3 and 6.30 g (50 mmol) of dimethyl sulfate and stirring was continued at this temperature under Ar.

The reaction was followed by TLC (EtOAc on SiO.sub.2) which showed the clean formation of a single product. After 72 hours the reaction mixture was poured into 1.4 liters of well stirred water and, after stirring five minutes, the product was allowed to settle. Decantation, followed by filtration and water washing, provided 3.76 g (8.8 mmol) of methoxyanthrapyridine. The structure of the product was determined by nuclear magnetic resonance spectroscopy, infrared spectroscopy, ultraviolet spectroscopy, and elemental analysis. ##STR80##

B. Preparation of an Orange Polymeric Dye

A 250-ml, 3-neck flask, equipped with overhead stirrer, reflux condenser, Ar bubbler, and thermometer, was charged with 1.19 g (15 mmol) of poly(vinylamine hydrochloride) prepared in Example I, 0.6 g (15 mmol) of NaOH, 1.6 g (15 mmol) of Na.sub.2 CO.sub.3, and 50 ml of H.sub.2 O. The mixture was stirred until a homogeneous solution was obtained (pH 12.6), at which point the solution was treated with 639 mg (1.50 mmol) of the methoxyanthrapyridine prepared in Part A, 10 mg of Cu.sub.2 Cl.sub.2, and 30 ml of pyridine. The mixture was lowered into a pre-heated bath (125.degree.) and stirred at reflux under Ar.

The following treatments were made to the reaction at the times indicated:

(a) 60 minutes, 1.5 mmol methoxyanthrapyridine, 20 ml pyridine;

(b) 120 min, 1.5 mmol methoxyanthrapyridine, 5 mg Cu.sub.2 Cl.sub.2, 10 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH;

(c) 210 minutes, 1.5 mmol methoxyanthrapyridine, 10 ml pyridine;

(d) 300 minutes, 1.5 mmol methoxyanthrapyridine, 5 mg Cu.sub.2 Cl.sub.2, 20 ml pyridine, 0.25 ml (3 mmol) of 12 N NaOH.

After 390 minutes the reaction mixture was filtered through a fritted funnel while still boiling hot and immediately diluted with 160 ml of boiling pyridine.

C. Workup

The 300 ml of deep orange solution (pyridine: H.sub.2 O, 5:1, pH 13.0) was added as rapidly as possible (no cooling) to 2.5 liters of rapidly stirred ice-cold acetone containing 50 g of celite. After stirring 15 minutes, the celite was filtered and washed with acetone (4.times.500 ml). The filtrate was examined by TLC which showed only monomeric materials.

The orange polymeric dye was extracted from the celite by eight consecutive treatments with one liter of dilute aqueous HCl (pH 3.5). This afforded 2.58 g of cationic orange dye. Elemental analysis showed that m=0.44 and n=0.56. ##STR81##

EXAMPLE XXIV

The red colorant of Example VII is employed as a dye for wool and hair. A solution of the colorant is prepared by dissolving 0.1 g of the product of Example VII in 50 ml of pH 3 water. Small samples of bleached human hair and white wool yarn are immersed in the colorant solution for 90 seconds at room temperature. Times from 10 seconds to 10 minutes may be used as well. The samples of hair and wool are removed, pressed between two filter papers, rinsed briefly in deionized water, pressed to remove rinse water, and allowed to dry at ambient conditions. The hair and the wool are colored red. A portion of each colored material is tested for color-fastness. When placed in water, there is a very slight, almost imperceptible, coloring of the test water, indicating that the polymeric colorant has formed a fast bond to the substrate.

If this experiment is repeated using other colorants prepared in the examples, similar results are achieved.

A plurality of colorants may be present in the dyeing solution. Suitable dyeing solutions are aqueous solutions which have acidic pH's, preferably from about pH 2 to about pH 5, and more preferably from pH 2.5 to pH 4.0. Also suitable are solutions having up to 80% of water-miscible organic liquids in these, preferably oxyhydrocarbon organics selected from among 1 to 4 carbon alkanols, 2 to 4 carbon alkandiols and 3 to 5 carbon alkanones, particularly methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, actone, and methyl ethyl ketone. The colorant solutions may contain from about 30 ppm wt of dye to about 1.0% by weight of dye with dye contents of 100 ppm to about 0.5% being preferred and dye contents of 250 ppm to 0.2% being most preferred.

Claims

1. The process for water fast coloring a proteinaceous fiber substrate which comprises applying to said substrate a solution comprising a solvent selected from the group consisting of water of pH 2.0 to 4 inclusive and a water-organic solvent containing up to 80% by weight of a member of the class of 1 to 4 carbon alkanols, ethylene glycol, propylene glycol and 3 to 5 carbon alkanones, and dissolved therein from 100 ppm to 0.5% by weight of a polymeric colorant comprising a hydrocarbon polymer backbone to which is covalently bonded through amine linkages a plurality (m) of essentially anionic group-free optically chromophoric groups and to which is also covalently bonded a plurality (n) of free primary or lower alkyl secondary amine groups, wherein n is not less than 1/2 m, and n and m are such that their sum is from 20 to 3000 and the polymeric colorant has a molecular weight of not less than 2000 daltons and thereafter rinsing the substrate with water and drying the substrate.

2. The process of claim 1 wherein said free amine groups are primary amine groups.

3. The process of claim 1 wherein n is from 1.2 to 4 times m.

4. The process of claim 1 wherein said polymeric colorant has the structural formula ##STR82## wherein R.sub.1 and R.sub.1 ' independently are selected from hydrogen and lower saturated alkyls of 1 to 4 carbon atoms; R.sub.2 and R.sub.2 ' independently are selected from hydrogen, lower saturated alkyls of 1 to 4 carbon atoms and phenyl; R.sub.3 is selected from a simple carbon to nitrogen single covalent bond, 1 to 4 carbon atom lower saturated alkylene bridges, and a phenylene bridge; R.sub.4 is selected from hydrogen and lower saturated alkyls of 1 to 4 carbon atoms; R.sub.5 is selected from a carbon to carbon single bond, ethylene, a 1 to 4 carbon saturated alkylsubstituted ethylene, a 6-8 carbon aromatic-substituted ethylene, a ##STR83## ethylene wherein R.sub.7 is selected from hydrogen, 1 to 4 carbon alkyls, and --O--CH.sub.3, an ##STR84## ethylene, and a nitrilo-substituted ethylene, Chrom is an essentially anionic group-free optically chromophoric group and n, p, and m are numbers such that n is at least 1/2 m and the sum of n+m is from 20 to 3000 and the sum of n+m+p is such as to assure a molecular weight of at least 2000 to the colorant molecule.

5. The process of claim 4 wherein in said polymeric colorant R.sub.1, R.sub.2, and R.sub.4 are each hydrogen, R.sub.3 is a carbon to nitrogen single bond, R.sub.5 is a carbon to carbon single bond and n is from 1 to 6 times m and p is from 0 to 2(n+m).

6. The process of claim 5 wherein the solvent is water of pH 2.0 to 4 inclusive.

7. The process of claim 5 wherein the solvent is a water-organic solvent made up of water and up to 80% by weight of a member of the class of 1 to 4 carbon alkanols, ethylene glycol, propylene glycol and 3 to 5 carbon alkanones.

8. The process of claim 1 wherein said proteinaceous fiber is wool.

9. The process of claim 1 wherein said proteinaceous fiber is hair.